Method for preparing homogeneous composition comprising oxidized petroleum wax and a polymer of a monovinyl aromatic compound



Ne firawing; Filed Nov; 7, 1957,- Sei'. No 694,917

4 Claims. (Cl. 260-285) This invention relates to the preparation of compositions from partially oxidized petroleum wax, and to the compositions thereby obtained.

It is known in the art to partially oxidize petroleum wax to obtain products having elevated saponification number, e.g. at least 30 mg. of KOH per gram, and typically in the range from 50 to 150 mg. of KOH per gram Such products are useful in various applications, eg as a constituent of emulsion polish compositions; The latter compositions may comprise for example an emulsion of oxidized wax, e.g. oxidized microcrystalline wax, in water, a suitable emulsifying agent being used to prepare the emulsion, eg an amine soap such as triethanolamine or a morpholine soap of a carboxylic acid such as stearic, oleic, linoleic, lauric, palmitic, or other organic acid. The saponifiable portion of the oxidized Wax has emulsion-promoting characteristics and assists in the formation of the emulsion.

A highly important property of oxidized wax is-its hardness. various applications, such as in emulsion polish composi- For example, such oxidized wax for use in' 2,944,039 new July, 5 0,

a 2 obtained by ordinary methods. For example when poly merizing a mixture having a ratio of oxidized wax to vinyl compound polymer of 2:1, 3:1, 43-1,-v etc. a non homogeneous product is obtained which at room tem* perature exists as separate phases, one concentrated with;

respect to vinyl compound polymer and the other con centrated with respect to oxidized waxjI-t is also'foundthat polymerization of vinyl aromatic compound in the absence of oxidized Wax, followed by blending of the polymer with oxidized wax, also fails to produce a homogeneous compositiom According to the present invention, compositions containing relatively small amounts of vinyl compound poly tions, preferably hashardness corresponding to a penetra f tion at 77 F. (A.S*.T.M-. Method No; D217-44T) of less than 10, and more preferably less than 5-," since harder waxes produce a more durable finish upon application of the polish to the surface to be waxed and evaporation of the water to leave a wax film.

Oxidized waxes, as originally prepared by oxidation, frequently have penetration substantially above the desired penetration. Accordingly, it is desirable to reduce the penetration of such oxidized waxes to that required for satisfactory use in various applications.

According to the present invention, compositions having very low penetration are prepared from oxidized wax by procedure including contacting the latter for a substantial period of time with a monovinyl aromatic compound under conditions normally productive of polymerization of such monovinyl aromatic compounds. It 7 has been found that a saponifiable product, into which quently desired that the amount of monovinyl polymer not exceed about 35 weight percentor the total-'com- 3;

chlorostyrene, 'o-ethyl-p chlorostyrene, o-me'thyl p-iso 1 methyl styrene, alpha-ethyl styrene, o,p=di'methy1-atpha='i methyl styrene, m-chloro-alpha-methyl styrene, p'-ch'lorone, p-is'opropyl-alpha-methyl styreue, j

position; :It. is found however that homogeneous com positions containing relatively small amounts of vinyl compound polymer rel ative.to oxidized wax cannot be mer are obtained by a plural stage process which involves first the polymerization of a mixture of a vinyl compound and oxidized wax, followed by blending of the product with additional oxidized Wax.- I Sufliciently small amounts of oxidized wax are employed in the polymerization mixture that ahomogeneous product is obtained.- Usually the ratio of oxidized wax to vinyl compound is not greater than about 1.5 1. 0n the other hand, the ratio is usually not less than about 1:5. The polymerization product is blended with a sufiicient additional amount of oxidized wax to produce a composition wherein the proportion of the composition which is attributable to the vinyl-compound polymer is at the desired level, preferably within the approximate range from 5 to 35 more preferably 10 to 30%. The proportion attributable to such polymer is that proportion of vinyl compound. polymer which the composition contains assuming that the latter is a physical mixture of oxidized wax with a homopolymer. of the vinyl compound Whether this assumption is correct,- or whether the composition contains a reactiontpgoductof .vinyl compound with theoxidized wax is, not definitely known," and is not essential to the invention fl.

The monovinyl aromatic compound .employedaccordinglto the invention is one having the formula where R is hydrogen, methyl or ethyl, A is hydrogen or halogen or an alkyl radical having not more than three carbon atoms, and B is hydrogen or halogen or an alkyl radical having not more than three carbon atoms. Examples of suitable monovinyl aromatic compounds are styrene, o-methyl styrene, p-methyl styrene, o-ethyl sty- :rene, p-ethyl-styrene, o,p-dimethyl styrene, o,p-diethyl styrene, pechlorostyrene, m-clr'lorostyre'neg' o methyl-p propyl styrene, alpha-methyl styrene, p=methyl=alpha alpha-methyl styre m-chloro-p-methyl-alphamethyl st'yrene', mixtures .;of

monovinyl aromatic compounds, etc. Styfeneislapreferre'd monovinyl aromatic compound. foriu'seaocor to the invention, and the invention Willb' further scribed with particular reference to this compound, Where styrene is referred to subsequently, it is to{he, understoodt-hatothr monovinyl aromatic compounds as f nese naphthenate. 1 v a t I The following example illustrates the invention;

' defined herein can be employed in its place or in admixture. therewith". 1

According-to the present inv'entionya mixture ofdlb; 'idized'waxiand' styrene is first subjectedg'to styrene-polyf merizing'conditions. Any suitable known conditions for polymerization of styrene can ,be employed. 'For-example; the mixture canbe maintained at an elevated temperature, preferably at least: 100 C. and preferably 'at atemp'erature andpressure such that the styrene isin: liquid phase, in the presence of a polymerization cat- 'alyst jsuchas 'ditertiary'butyl peroxide, benzoyl peroxide;

The oxidized wax used according to the invention may i have 'beenprepared by any suitable method. Commonly employed conditions for oxidation of wax include oxidation temperaturewithin the rangefrom 200 F. to 300 F., oxidation pressure within the range from atrnospheric pressure to 500 'p.s'.i.g., the use of a free-oxygen containing. gas, e.g. air, oxygeniozone, ozon'ized air, etc. as .oxidizing agent, and the use of an oxidation catalyst of the wellknown metallic oxidation 'catalyst type, eg. mangag Example I :7 ;A partially oxidized microcrystalline wax having 'sa-.

ponification number of 85.7, acidnumber of 22.7, penetration at 77 (A.S.T.M. 13217-441) 'of 6, and

viscosity at2.10 F. of 55 2's econds was prepared by oxidation' of microcrystalline wax at250 to 270 F. with air'for 203.5 hours in the presence of manganese naph thenate in amount such that theoxidation mixture con- 1 tained 0.04 weight percent of manganese.

2S0. grams'of' the partially 'oxidized wax were heated' 'together:with IOQmlQofSX lene underrefinxing condie "tions' with mechanicalstirring." To the heated solution V of oxidized {wax'in ay'l ne; 25 0 gram's, ofstyrene contain-j ing' 2i 5igramsfotf ditertiarybutyl" peroxide were: added i I dropwise with The reaction mixture was. refiuxed forQSjihours; 'Ihestirrerj and .condenser'were: then removed; the contentsof the flask'heatedio'a' liquid temperatureof 1 60 .C; at 25 mm. of Hg to remove nnreacted'styrene andxylene. 4675 grams of a homogeneous productwere' left as residue. This prodnot was allowed to stand overnight at 100 C. No sepa ration into layers occurred.-- The'following table shows a comparisonof the properties ofthe original oxidized wax and the product obtained; 1

Weight, Sap Penetration g. No. 21:77? Original oxidized wax 250 85.6 7' Product 467. 5 43. 8

100 mm, by weight of productwereblendedin thliquidstate with 100 parts-bymeight ofjtheforiginal,. oxidized} wax havingpenetrationiot e ..-t o. obtai ho 'mogeneous'producthaving penetr ation 'ot 2. 100 parts byaweight ofthe latteripi'oduot were blendedwithj 100 "additio naljparts hy weightfofj the originalfoxidized wax. I to obtain a homogeneous pfoduet having penetration o f..4'. :1 1: .jlhesefi'esultsf'show' that 'pioductsjobtained'Ihy; poly;

ri zation :of; styrene in the presence of oxidiz n bl nded gvvitli ddi otjpiiefornied I tionalloxidized EW'ax Howe he began f I btainedj 7a *"a ea i s i Heterogeneous products were merization of 200 grams of partiallyioxidized'petroleum microcrystalline, wax having saponification number of 99,

, mg. ot:KOH per gram, acid number of-43 mg. of KOH- I perature, and generally'be within the range {m "StoSO houISP- I per gram, penetration at .773. F. .of 22, SU. viscosity at 210 F. of 259 and melting point of 173 F.', together with 50 grams ofstyrene, the polymerization being conducted in the presence 05100 grams of xyleneunder re: 'iluxing conditions .(vapor temperature .l38 (3.). for 1.1"

hours. in the presence of one gram of ditertiary butyl t p'efoxidez' the product, 'after stripping out xylene and cooling to rooni temperature, separated into two layers each constituting about 'one-half of the total product In another experiment where 2501 grams "of l styrene were 2 employed per sou-grammar thesame oxidized wax; the

products separated at 175 F. into, a solid layer having saponificationmumber of 43.7 and'weighing 319 grams a and a liquid layer having saponification number of 83.21

and weighing 403.6"grams; 1

According to the present inventiomproducts'having saponification number'in the, range from 20 to 120 nig .of KOH per gram, and penetration at 77 P. less than.

The'inventionclaimed y w 1. Method foipreparation: ofqsaponifiable materials" havinglovn. penetration which comprises; contacting par- 15 can be prepared from oxidized waxeshaving greater penetration and saponificationinumberl .The hardest products according to' the invention, those having pene tration less than 5, may have saponification number in' the'range from'20to 80. Products having sapo'n'ificaa tion numbers and penetrations outside the 1 above-specie fied ranges can also bepre'pared'according to the inven tion.

In' the preceding fexample, oxidizednncrocrystalline' wax was treated according to the invention. Pa'raflin' waxes can also be beneficially'hardene'd by the'process ofthe'invention. I z gr This application is a. continuation-in-pantof copend- 7 ing pplication SerialNo. 374,148, 'filed August 13, 1953', by the presentinventor; and now abandoned? tially: 'oxidizedipetroleum fwaxhaving sap'onificationjmini gram with a nionovinyl aromatic compound having the." following formula?" 7 i: if a where R is selected the group consisting of ,gen, methyl and'ethyl radicals,' A is selected from the roup consisting' of hydrogen, halogen and alkyl radi i V cals having '1 to 3 carbon atom in c'lnsive aad' His sive, the contacting Y being selected from'the groupponsis ting ofhydrogen, halogen: I andalkyl radicals havingll to'3i. carbon immanent:

' rfor me d i isjlelqf conditio s imonovinyl aromatic vinyl aromatic compound in: said contactingbeing wi tinnljwith themonovin "areiitmc iiinpauhd"5015mm 100 C. in liquid phase in the presence of a polymerization catalyst.

References Cited in the file of this patent UNITED STATES PATENTS 1,983,672 Labarthe et a1. Dec. 11, 1934,

2,127,381 Herrmann et al Aug. 16, 1938 2,733,224 Smith et al Jan. 31, 1956 FOREIGN PATENTS 649,013 Great Britain Ian. 17, 1951 

1. METHOD FOR PREPARATION OF SAPONIFIABLE MATERIALS HAVING LOW PENETRATION WHICH COMPRISES: CONTACTING PARTIALLY OXIDIZED PETROLEUM WAX HAVING SAPONIFICATION NUMBER WITHIN THE RANGE FROM 30 TO 150 MG OF KOH PER HRAM WITH A MONOVINYL AROMATIC COMPOUND HAVING THE FOLLOWING FORMULA: 